Dodecahydrododecaborate compounds



and Hg.

Unit-ed States Patent-Q 3,169,045 I DODECAHYDRUDGDECABORATE COMPOUNDS Henry C. Miller, Wilmington, Del and Earl L. Muetterties, West Chester, Pa., assignors tov E. I. du Pont' de Nemours and Company, Wilmington, Del., acorporation of Delaware 1 No Drawing. Filed May 20, 1960, Ser. No. 30,442

V 10 Claims. (Cl. 23-14) This invention relates to certain new polyhydropolyborate salts and to methods for making the same. j

Compounds of boron and hydrogen whose properties are described'in the literature are limited to products havingat mostlO boron atoms. The known covalent hydrides include such compounds as B H B H B H Th known salts of boro'hydride anions in- B H v- Salts of borohydride'anions having more than 10' boron atoms are unknown. Salts' of known. borohydride anions decompose readily in acid solution and, in fact, the acids of borohydrides were heretofore unknown.

In particular, this invention is"directed to a class-of. polyhydropolyboratesv characterized by the generic formula (1) Mm ans where M is a cation having a total atomic w eightof at. least 5 and, further, having a valence of less than 5,

(B H is an anionhavingajvalerice of 2; a and-b are each positive whole numbers of through 3 (i.e., greater than and less than 4-) whose respective values arede termined by thevalence of M. V v V In'Formula 1, the term c ation.has reference to an atomor group of atoms with atotal atomicjweight of at least 5 which," in aqueoussoluti'on, forms a positively charged ion. Examples of suitable cations include metals,

substituted ammonium, N-substituted 'hydrazonium, subderivedg enerally from any metal. The metals according to-the Periodic Table in-Demings General Chemin 'Langes Handbook of Chemistry)? 9th ed., pp. 5 6-57",

3,i59,li45 Patented eb. 91, 1965 A further group of particularly useful products are. dodecahydrododecaborates in which the cations are derived, directly or indirectly, from nitrogen bases, e.-g.-,

to nitrogen. The R groups are not critical features of these cation groups; thus, R can be an open-chained,

1 closed-chained, saturated or unsaturated hydrocarbon or substituted hydrocarbon group, or R can. be a heterocyclic' ring ofwhich the nitrogen atom is a component part, such as pyridine, quinoline, morpholine, hexarnethyleneimine, and the like. Preferably, R, for reasons of availability of reactants, contains not more then 18 carbonatoms. R can be, for example, methyl, Z-ethylhexyl,

octadecyl, allyl, cyclohexyl, cyclohexenyl, phenyl,- naph thyl, anthryl, cyclohexylphenyl, diphenylyl, benzyl, chloroethyl, w-cyanoamyl, beta-hydroxyethyl, p-hydroxyphenyl, and the like. The aryl group in the aryldiazonium ammonium (NHJ), hydrazonium (NH NH N- stituted phosphoniinn,"aryldiazonium (aryl-N=N+,),and".

' the like.

. r Y H40 Metal cations 'in the compounds of Formula l can be Handbook Publishers, Inc. (1956), are the elements of} Groups 1,,1 vm, Ii B-, Iv]-B, v-B; VI B, vii-B and the 1 elements 'of Groups I IIA, IV A, V A, andVlg-A which; have atomic numbers above},14,33"and 52,;respective-. ly. These metals in'clude'both light and heavyfmetals.

cation preferably contains at most 18 carbons, e.g., a terphenyldiazonium group.

'Examplesof N-substituted hydrazonium radicals include those wherein R has the same significance as indicated .in the preceding paragraph. To illustrate, the

hydrazonium cation can be derived from phenylhydrazine,,

methyl hydrazine, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine,'ethylhydrazine, 1,1-diethylhydrazine, and similar compounds. Examplesof aryldiazonium radicals inj elude phenyldiazonium, tolyldiazonium, p-eth'oxyphenyldiazonium, and the like, I I

Thus, the atomic weights of nitrogen bases from which cations are derived canrange from a low value of about 17 for ammonia '(NH fto a value as high as about 800 or even higher for long chainsubstituted nitrogenbases,

'e.g., trioctadecylamine. a

The nitrogen bases ca'nbe polyba sic, i.e., the bases can form' cations ,having'valences of 2, 3, and higher. To illustrate, i;polybasic nitrogen compounds whichcan be employed to form salts includediamines for example,

"lhexamethylenediamine, p-phenylenediamine or pipera- The light metals are also known'as the "alkali metals and;

the alkaline earth metals. The heavymetals include brittle, ductile and low-meltingmetals as described in the above-mentioned Periodic T able in Langes Hand-i book of Chemistry. Metals having a wide range of compounds of Formula 1. e p

Preferred metal cations are derived from the elements of Groups I-A, ILA, LB and IIB having an atomic number up to and including SQ, inclusive.

bismuth or even higher, are operable as cationsiin the pounds are dodecahydrododecaborates having ascations' Li,"Na, K, Rb, Cs,

Most preferred metals for use in the compounds of this' invention are the light metals (the alkali and alkaline earth metals of.GroupsIA andII-A) having. an atomicnumbet less than 87, i.e.,.lithium, sodium;potassium,rubidi um, cesium, beryllium, magnesium, calcium, strontium,

and barium. z

The lithium, silver, and mercury dodecahyd'rododeca-" borat'esform an especially preferred group of salts.

zine) triainines (forexample, diethylenetriamine), tetra- 'mines- (for example, triethylhetetramine), and the like- The valence of the cation M will bebetween l and 4, 7 i.e., M can have a valence of'l,'2, 3 or 4; In most cases the valence of ,M will be lo'r 2 and thisgroup of compounds in which the valence of M is at most 2 are readily nrepa'rableyand' so form a preferred group ofcompounds inthis invention.,, Y r

The group'M canbe acjombination of cations whose total ator'nic weight is at least 5. To illustrate, M can be two'nronovalent metals or a monovalent metal and y g o 12 12) or 12 1 2 more simply, NaKB H and KHB H As a further illustration, M canbe a complex cation such as ammino metal groups, eg'., (NH ),,Y, where Y is cobalt, nickel,

copper, zinc, cadmium, mercury or silver and n isa positive number of at most 6. Compounds ofthe invention where M is an'ammino metal group, as discussed above,

generally have low solubility in water and they are of particular interestbecause ofthis property.

The valence of the ,polyhydropolyborate anion in Formula 1 is 2. The values of a and b, therefore, in the genericformula' are determined by the valence ofv M,. i.e., a multiplied by thevalence of M is equal to 2b.

' dodecaborates.

a valenee of M The values of a and b are the smallest numbers which satisfy the equation and these values lie between 1 and 3.

Examples of new compounds of the invention, illustrated by formulas, are as follows: Li B l-l Na B l-l K2B12HI27 m m iz ial Bm zl is rz M 12 12) 2( 12 12)3, 2( 12 12)a, rz u 12 12 c is iz a iz rz 312 12 rz w H IZ; 2( 12 12)3, 12 12 m m 2( 12 12)s, 4)2 12 12, 3)4 ]z 12 12, 3)3 2 12 12,

' z s ah m iz; B 17 3)2 12 12 [(C18H3'7)2NI'1Z]2B12H12 '(rw mh m m G lQZ QJ IZ IQ: (NHTNH3)2B12H12 In general, the new compounds are usually solid products which are salt-like in character. 'Many of the compounds dissolve in water or hydroxylated solvents. The majority of the compounds are white crystalline materials which are generally stable at normal atmospheric temperatures and pressures. The compounds, as obtained, frequently contain water or solvent of crystallization.

further shown by Compounds in this form are included within the scope of the invention. Solventsof crystallization are readilyremoved, as described later, by conventional procedures,

I I g 3,169,045

where M is an alkali metal or alkaline earth metal and a has a value of 1 or 2. As will be disclosed below, these products are then further reacted with an appropriate salt or base to combine the desired cations with the dodecahydrododecaborate anion.

The reactants used in these processes of preparing the compounds of this invention are commercially available. Any alkali metal 'or alkaline earth metal hydroborate can be used, but sodium and potassium hydroborates are the most readily available salts and they, therefore, form a preferred group.

The alkali metal and alkaline earth metal hydroborates employed are also referred to as metal borohydrides and they can be represented by the general formula:

( T UX where M is selected from the group consisting of alkali metals and alkaline earth metals, and'x is a positive whole number 1 or 2, i.e., x represents the valence of M.

Alkali metal and alkaline earth metals are, of course,

elements of atomic numbers 356, inclusive, of Groups I-A and II-A of the'Periodic Table. M can be, for example, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium. When M is an alkali metal, x has a value of 1; and when M is an alkaline earth metal, x has avalue of 2.

Diborane, the second reactant in these processes, is

represented by the formula, B H

e.g., recrystallization, heating under reduced pressure, and

the like. The tendency of the salts to crystallize with solvent of crystallization or water of hydration makes it difficult I at times to identify accurately the composition of the for the heretofore unknown B H anion appear con-' sistently in hydrate-free salts, hydrated" salts, and salts having other solvents of crystallization. I v

In the infrared absorption spectra of some of the dodecahydrodecaborates, the absorption at 4.0; appears as In general, commercial grade materials are satisfactory for use in these processes without special purification. f It is, of course, preferable that the reactants be free of adventitiousmoisture which, if present, may lower the yield of desired product.

been formed. As a matter of convenience, the reaction is frequently conducted under autogenous pressure in a suitablep'ressure vessel. In this mode of operation, a pressure vessel is employed which is lined with a corrosion- "resistant material, e.g., commercially available stainless; "steels, platinum or silver. The pressure vessel is preferably flushed with an inert gas to remove adventitious moisture and it is then charged with an alkali metal hy droborate and, optionally, with a solvent. The vessel is closed and cooled to a low temperature with, e.g., liquid a doublet in which there is a shoulder on the 4.0 1. band i compounds has been adopted at the present time. The

nomenclature used herein follows the proposals made I by a group of the Committee on Nomenclature of the American Chemical Society Division of Organic Chemisthe present invention will be referred to as dodecahydro dodecaborates (2*), employing the appropriate conventional name for the cation, e.g., disodium dodecahydrododecaborate (2"). For simplicity, the anion valence,

(2), will be omitted, but it is understood that this des-.

ignation is implied in the name.

The compounds of Formula 1 above can be made by processes which involve the reaction of an alkali metal or alkaline earth metal hydroborate and diborane to produce alkali metal or alkaline earthmetal doclecahydrothe formula:

(2) Mutants) These compounds can be represented by nitrogen, solutions of 'solid carbon dioxide, and thelike. The vessel is connected to a vacuum pump and their ternal pressure is reduced to a value sufiiciently 10W, e.g., 1 mm. or less (as low-as 0.001 mm.), to permit the desired quantity of diborane to be pressured into the reac tion vessel. The reaction mixture'is held at 0 C. or

higher for the period necessary to effect reaction. The

sirable to use diborane in considerable excess, i.e., the,

molar ratio, B H /MTBHQ is preferably 2 or 3 or even higher. It is not necessary, however, to use these ratios to obtain at least some quantity of the desired polyhydropolyborates.

At C., or higher, the principal product is a polyhydropolyborate having at least 12 boron atoms and,-

generally, although not necessarily, an equal number of hydrogen atoms. A principal product at the higher temperatures of operation is a dodecahydrododecabor'ate salt I of-Formula 2. u

Heating of the reactantsimay be accomplished by any suitable means; The temperature maybe raised by at reached by a one-step process.

stepwise procedure or the desired temperature may be It is essential that the reaction be conducted at a pressure higher than atmospheric) Accurate control of the pressure is not necessary and autogenous pressure obtained in the reaction chamber is normally used. This pressure may lie between about '3 to, 500 atmospheres (absolute) or even higher.. It is preferable that the reaction be conducted at a pressure of 5 -atrnospheres(absolute) or higher. j

Mixing of the reactants during the process is desirable although not essential. Mixing can be accomplished by any suitable means, e.g., by mechanical stirring, shaking or tumbling of the entire reactor. i

The time of the reactants during the process is desirable although not essential. Mixing; can be accomplished by any suitable means, e.g.,:by mechanical stirring, shaking or tumbling of the entire reactor.

The time of the'reaction is notcritic'al... In a batch process, the time will generally lie between about 1 hour and 50 hours, In general, a reaction time of 5 hours to 25 hoursis sufiicient forbatch operation. .For a continuous process, which can also be employed, shorter redrate, in the form of a white crystalline solid. The acid,

' invention are useful as sequestering agents for metals,

action times are used and unreacted components can be r recirculated.

In working up vthe reaction products, the volatile reaction products are generally removed by venting the vessel to-the atmosphere. ,qHydrogen is a by-product of the reaction and it is removedwith the volatile; products.

Suitable precautions shouldbe observed inventing the reaction vessel in view of the flammability, ,toxic or, possibly, explosive hazards otthe volatile products;

The reaction products, left afterventing, are generally liquids or solids. They'canmbeseparated and purified, by conventional procedures, .e.g.; filtration, crystallization,

solution chromatography, and the like. The products shouldbe handled with the customary precautions ob served in handling chem'icalicoinpounds to prevent'undue contactwith the skin or inhalatioiiof fine powders; 1

In a preferred form of thes'e processes," the: reaction." between dibora'ne' and thealkali metal or alkaline earth metal hydrobo'rate is conductedYin the presence .of an inert solvent, i.e., a liquidwhich'is unreactive .underithe conditions of the reaction with the components ofithei process and with the products which are derived. Ethers, thioethers (i.e., sulfides), tertiary amines, trisubstituted phosphines and hydrocarbons can-be used in the process.

The solvents preferably are liquids at'the operating ternperature and, in most casesg'ar'e liquids at prevailing atmospheric temperatures. Examples. of operable solvents are diethyl' ether l.,2 dimethoxyethane (glyme),

1,2-diethoxyethane, benzene,,-heaane triethylamine tributylarnine, dimethyl" sulfide, dibutyl' sul fide -trithylp'hosphine, tributylphosph'inefand the jlikefiEthersind tertiary amines are preferred, olyentslf Relatively. high boiling ethers .or amines, s'ui'zh as glyine or' triettiylanline,

The alkali metaland alkali ne' earth metal dodeca'liydro dodecaboratesgcan be employed git) preparfe'co'rjnpoui'idsof Formula 1Q For example, anaqu'e'ous solutionof analkali metal or alkaline earth'rnetal ';salt is contacted wither strong acid or with a strongly of metals, salts of n1etals?( botl1organic and inorganic), nitrogen bases salts of nitrogen bases both organic and inorganic), andsirnilar types of compounds to obtain dodecahydrqdodecaborates which. have the desired ication In'aprocess employing an ion exchange resin,

M. strongly acidic resins of the" sulfr'anicacid variety are skin. of Na s n is passed'through a column packed c cation exchange resin.

to obtain the free acid, H B H L The acid, generally in solution, is reacted with oxides of metals, hydroxides 65, determined by the valences of-MLand (B H n is an in aqueous solution, can be reactedwith'nitrates; chlorides, bromides, acetates, benzoates and similar salts of metals or other bases to obtain salts of Formula 1.

In a second mode of operation the alkali metal and alkaline earth metal dodecahydrododecabonates can undergo simple metathetic reactions with other salts to eifect an exchange of cations. Thus, Na B H can be reacted witlihminoniurh' sulfate, pyridinium chloride, morpholinium sulfate, silver nitrate and ferric sulfate in aque ous or non-aqueous solution (e.g., methanol) to form dodecahydrododecaborates having as'cations ammonium,

pyridiniurn, morpholinium, silver and iron. These illus-' trations are not limiting and they demonstrate the breadth of metathetic reactionswhich can be used;

The novel products obtained by the processes of this especially heavy metals.

To illustrate, a mixture of hydrocarbons in the boilingran'ge of gasoline, which contains in solution a copper salt of an organic acid (copper stearate), is thoroughly agitated with an aqueous ammoniacal' solution of Na B H The hydrocarbonlayer, which ;is s e pa-: rated from the aqueous reagent, is completely free of thedeleteriolls copper salt. v

.The new compounds are useful as sequestering agents for metals in aqueous media. Thus, copper, nickel, cobalt, zinc and cadmium are removed from aqueoussolutions -of salts containing these metals by; mixing the borate, e.g., c BizHiz- The ammonium, tetra'methylamrnoniurii 'a'nd, fin general,"hitrogen-base 'salts are also useful infthe'fieldfof sequestering'agents to remove undesirable metals from aqueous or hydrocarbon media; Inaddition to the metals named inf the preceding paragraphs',-i silver ions-fare re; moved from solutions containing them by treatment withv Na' B 51 1 Mercury anions are removed by treatment with "ammoniacal solutions of dodecahydrododecabfor 'Ther'dia'zonium' salts, when heated orf struck, dec

, compositions"employedras explosionjiriitiatorsl V Y In the especially pjre'ferr'edf group of salts, 'lithiumf dodecahydrododecaborate is usefuhfor' modifying the combustion characteristics or hydrocarbon fuels; 'silver dodecahydfododecaborate is useful in the-field of lightsensitive chemicals employedin photography; and nner curydode'cahydrododecaborate'jjis useful in biochemical 7 applications for which mercurycompounds are frequently empl yeest The invention is following examples. in each of'the examples the prod-- wherein M is selected from the'group consisting bf alkali" metals and alkaline earth metals, (B H is an anion having a valencaof 1-3, inclusive,- a' and b"-are"positive Whole numbers of 1 through 3 whose values are integer of at least :3, 1m is aninteger greater than 3 i and is at least equal to ri, andithe sum of m,j*r t, and

preferredlbecause ofavailability, "e1g, AmberliteflR- l20H-.and.'Doweir 50. To illustrate, an aqueous soluwith Amberlite, ,IR-lZO-EL. f The 'eluent, ,whichgcom tainsthe acidI-I Bi H Q, is evaporated under reduced pres-" 7 the valence of (B fimlisa positive even number, v

The valence of. M"'o an,;be 1 or 2, and the value of n can range up to 14', 20, or even more. The relationh p between a and b' is" more particularly expressed by 4 4 (a-mi po's'e withirapid energy release and they are useful in} further illustrated reference 'totthe gen andno diborane.

' tiori spectrum.

' 7 Note that the value of m be equal to or greater than n but never less than n.

The composition of the hydroborates obtained in the process can be controlled by conditions'under which the reaction is conducted so as to fix the atomic ratio of boron to hydrogen.

' Example I A pressure vessel (capacity, 80 ml.),' is charged with 1.9 g. of sodium hydroborate, 2.8 g. of diborane and is at least 4 and that it can reaction vessel is cooled and it is vented to remove volatile products. It is noted that these products contain about 0.187 mole of free hydrogen and no diborane."

C, 17.20; H-,-8.40; B, 41.27; Na, 16.74. Found: C, 17.07;

H, 8.36; B, 40.66; Na, 16.5.

The compound shows/the characteristic infrared ab-- sorption spectra of the B ll anion, i.e., .bands at 4.0 1.101 and 9.35,u, '-0.1 and it is; therefore, evident that the product on the basis of the infrared-absorption spec trum and elemental analysis is disodium 'dodecahydrododecaborate (2-).-

Example II I Using the procedure described in Example I, a mixture of 1.9 g. of sodium hydroborate, v10 ml. of dry ethyl ether and 2.7 guof diborane is heated for 10 hours at V 100 C. underautogenous pressure-The volatile prod ucts obtained in the reaction contain 0.2 mole of hydro- A solid product in the reaction vessel is collected, washed thoroughly with dry etherand' dried to give :2.6' 8 g'. of a whiteso'lid. The infrared ab- 'sorption spectrurn of thelsolid shows that it is'a mixture of .s'odiuni hydroborateand' a disodium polyhydropolyborate (2-).' Crystallization of the crude. product from f a mixture of tetrahydrofuran andglymeyields'adisodium polyhydropolyborate (2 containing 1 m ole of glyme and 1 mole of water of crystallization. The compound has the. formula Na B H rC H O -H G, asshown by the characteristic absorption bands in the infrared absorp- Example ,1 a H 7 ,Using the procedure described in Examplel, a mixture of 1.9 g. of sodium hydroborate, 2.8 g. of diborane and i "10- ml. of dry triethylamine fis heated for,-10 hours ,at' 120. C. under autogenous pressure-. The volatilej -reactionproducts contain 0.18 mole of hydrogen. The'nonand a quantity (2.64 g.) of insoluble material is separated by filtration. The solid is extracted with hot tetra;

hydrofuran, leaving 0.74 g of unchanged sodium hydroleaving 0.21 g.- of a disodium polyhydropolyborate, i.e., I

disodium dodecahydrododecaborate' (2). Q Example V.

' A. A pressure vessel of 400 ml. capacity is charged with9.5 g. of sodium hydroborate and .75 ml. of glyme. The vessel is closed, cooled to 80 C. and evacuated to a pressure of about 0.001 mm. of mercury. Diborane (14.0 g.) is charged into the vessel which is then sealed and heated with agitation under autogenous pressure for 10 hours at 120 C. The molar ratio of NaBH to B H in this reaction is 1:2. The reactor is cooled, the volatile products are released by venting and the contents of the tube are washed into a receiver with glyme. A suspension of a white solid in a yellow liquid is formed from which the solid is separated by filtration. The solid is dissolved in hot tetrahydrofuran and the solution is filc, 15.37; H, 7.98; B, 46.67; Na, 16.49).

The compound-can be obtained as its hydrate, free of ether of solvation, by recrystallization from a large quantity of diethyl ether or tetrahydrofuran/ diethyl ether mixtures. The ether-free hydrate has the formula I 32 12H12 H2 1 and itsinfrared-absorptioncharacteristics are as follows:

' 2.8a, sharp, medium; 3.9a, sharp, strong; 6.2a, sharp,

medium; 9.25 sharp, medium; and l3.9a,"broad, medium. *Analysis.-.-Calcd for Na B H -H O: H, 6.85; B, 63.05;-Na, 22.32. FoundLH, 6.56; B, 62.02; Na, 20.5;

B. The procedure of Part A is repeated, employing 9.5 g. ofsodium hydroborate and 26.0 g. of diborane. The molar ratio of NaBH to 13 1-1 is about 1:4. There is obtained 10 g. of a disodium.polyhydropolyborate which is shown tobe disodium dodecahydrododecaborate (2*) and g. of another disodium polyhydropolyborate (2).

.. The latter compound yields 30 g. of highly purified product on recrystallization.

Example Using the procedure of Example I, a mixture of 1.9

V g. ofpsodium hydroborate, 2.8 g...of.diborane and 15 ml.

. of benzene is heated for 10jhou'rs at 120 C. under autogenous pressure. The volatile reaction product contains] 0.19 mole of hydrogenand nodiborane. The vessel containsayellow solid suspended in a clear liquid. The solid borate. Glyme is added tothe tetrahydrofuran filtrateto form a precipitate whichawhen'separatedand purified in.

the usual-manner, yields2.0 g. of a disodium polyhydro- N z iz iz- I Example I-V polyborate which is i A mixture of 1.9 gIof sodium hydroborate hours at 120C. under autogenous pressure. A small amount of diborane and 0.145 mole of hydrogen is-re-.

isfremoved by'filtrationand washed with glyme. The infrare, c l absorptionspectrumiof the solid shows that it is prlnclpally a disodium ,polyhydropolyborate (2) with "somerunchan'ged sodium hydroborate, i.e., disodium dodecahydrododecaborate (2) with-a minor quantity of sodium hydroborate.

and zs of diborane is hfated,,as described in Example I, for 1 0 covered in the volatile reactionproducts. A solid which forms in the reaction vessel is removed, washed with ether Y ExampleVlI "Using the procedure of Example I,.a mixture of 2.8

' g. of potassiumhydroborate, 2.8g. of diborane and 15 ml. of glyme is heated for 10 hours at 120 C. under autog- V enous pressure. A total of 0.281 mole of hydrogen is formed. fiThe yellow solidin the reaction vessel is collected'onla filter and it is washed with glyme until it is colorless." The solid is dried under; very low pressure (less than 1 mm. .of mercury) at C. to yield 3.93

,g". of dipotassiuni polyhydro'polyborate-,(2), i.e., dipotassium dodecahydrododecaborate (K 3 21 1 scribed in Example 15 mll'of dimetliyl'lsulfideand mixturefis heated 120?.Cj-forf lhours vvith agitation.

products are removed as described in Ex he I volatile prdductsjfcontaiii 0.123. m'olel .-fura1i7glyrne mixture. Afterj dlryi v is NaB H containing g'lym I weighs 1.57gl

- 'iHi strat'ed imEX mPl One-half of the above solid product is dissolved in water and aqueous tertamethylammonium chloride is added to the solution. A white solid separates which dissolves in completely when the'solution is heated to boiling. The solution is filtered and the filtrate is chilled to precipitate bis (tetramethylarnmonium) dodecahydrododecaborate (2-). There is obtained 0.38 g. of the product which has the formula [(CH3)4N]2B12H12.

" Example VIII The gases contain 0.19 moles of hydrogen. A white solid suspended in a yellow liquid remains in the reaction vessel. The mixture is filtered to separate the white solid which is washed with glyme' and dried at low pressure (0.001 mm. or less) at 90l00 C. There is obtained 1.61 g. of Na B H containing glyme of solvation. The identity of the product is confirmed by the infrared absorption spectrum. 1

Example IX A pressure vessel (capacity. 400 ml.) is. charged with "19.0 g. sodium hydroborate and 75 ml. be dry triethylamine. The vessel is cooled in a solid carbon dioxideacetone bath and the internal pressure is reduced to less than 1.0 mm. pressure'by means of a. vacuum pump. Diborane (36.0 g.) is introduced into the vessel which is 'then closed] The mixture is L'heated withagitation forhours at 180 C. After cooling the vessel and ventving to remove volatileproducts; there remains a solid resi- I due which iswashed from the vessel with glyme. The

solid is separ'atedby filtrationfand it is again'washed with 1 glymel The washed solid is dissolved in hottetrahydro- 10 at 100 C. The volatile products obtained on venting the reactor contain 0.12 mole of hydrogen. The reaction vessel contains 1.72 g. of white solid and approximately 0.9 g. of unreacted. sodium metal. A portion (0.5 g.) of the white solid, which is shown by infrared spectrographic analysis to contain disodium polyhydropolyborate (2") is dissolved in water and the solution is treated with excess aqueous tetrarnethylammonium chloride. There is obtained 0.2 g. of bis(tetramethylammonium) polyhydropolyborate (2*). The compound has the formula iQs lz m rz- I Other precursors for alkali metal hydroborates which may be employed are alkali metal hydrides and diborane or a combination of an alkali metal, hydrogen and diborane.

In Examples I through XI the principal product which is isolated and characterized is a salt of dodecahydrododeis isolated and characterized is a salt of dodecahydrododecaborate. However, as stated previously, the process yields a broad range of polyhydropolyborates represented generically by Formula 4. The preparation and isolation of a representative polyhydropolyborate, falling within the broad scope of compounds of Formula 4, i.e.,

- sodium octahydrotriborate, is illustrated inExample' XII.

Example XII autogenous pressure.-

: The vessel is cooled and it is vented to remove volatile material. 7

reduced pressure (lessthan 1 micron) at the prevailing atmospheric temperature (about 25 C.) until all volatile material is removed. There remains 9.2 g. of oily product which 1S sodium octahydrotriborate containing glyme.v

(B) The process of Part Ais repeated employing 1.9 g.

(0.05 mole) of sodiumhydroborate, 1.8g. (0.06'mole) tity of insoluble product. I Thefiltrate is heated to boiling and glyme is. added slowly until solid material. begins to separatef. The mixture is chilledand it is .then f ltered.

to separate the white crystals;- Thesecrystals are washed.

with 'glyme and dried at less ihanfQOQlmm. pressure at C. to yield 43.9 g. of fia B H containing glyme andwateI-of'solvatiom.; treatment of't yields an, additidnal the produc't.

7 Example X A pressure vessel. (80}mli capacity) 'is charged'as deand the'vola I i u M i m 'ethyl sulfide isjrern i'edl from the resi due inthe reaction'vessel bydist'illation a whiteisolidiw 1 In the operationof the; proc precursors of I the alkali; heta yd niborjaie i ployed; e.-g.%, an -alkali metal and dihorahe; the, alkali metal'hydroborate. This 'm de 6 25 I CLunder autogenous of diborane and 10 ml of glyme. The mixture is held at pressure (about 18 atmospheres gauge) for 10 hours. Thevolatileproductscontain 0.04 mole of unreacted diborane and 0.05 mole of hydrogen.

The residue is a clear liquid which, followingjevaporation of thesolvent, leaves 6.4

g. of sodium octahydrotriborate contammgglyrnefi I V (C) A water's olution containing 5 g. oftetramethyl ammonium chloride-is added to an aqueous solution of the sodium octahy'drot-riborate obtained in Part 1A. A while S OllCl separates which redissolves uponheating the product is obtained from several crystallizations. The

dentity of the compound, which has the formula v of cesium octahydr'otriborate (1*),i..'e.,.CsB H gz zr lysjsfCalcfd forCSBHitl ice bath, Tetrarnethylamrho'nium octahydrottiborate (1*) separates as white "crystals. A total. of 4.97 g. of

I. a)4 3 a is. confirmed by theinfrared absorption spectrum which 1s;1n' agreement (1-) salts-5 2 Theoilyi product' obtained initially in the reacti on is ,convertedflto other metal salts by reaction with theapprppriate chloride. T o illustrate, a methanol solution conta'ining 083g. of the oily product is mixed with an equal I u The mixture is heated to re fluxand just "enough water is added to form a clear solutio'n; .{Thehotl'mixture'is chilled in an icefbathl'and dense f; crystalsgform jwhichare separatedf'by filtration. rystalsare washedand .dn'edaird there is obtained 0.35

weight of, cesium chloride.

An amber'liquid remains which is held under u V The hot solution is; mixed with' an equal volumeof methanol and it is their chilled in an with data reported for octahydrotriborate.

The"

does not yield the desired polyhydropolyborates. To illustrate, a vessel is charged with 0.95 g. of sodiumhydroborate and ml. of dry glyme. The charged vessel is evacuated to about 50 mm. pressure and sufiicient diborane (0.8 g.) is added to bring the pressure in the vessel' to 1 atmosphere (15 lb./sq. in. absolute) at the prevailing temperature, i.e., about C. The vessel is closed, placed on a mechanical shaker and agitated at 25 C. for about 4.0 hours. The internal pressure remains unchanged at 1 atmosphere. All'of the diborane is recovered unchanged and no hydrogen attributable to the reaction of diborane With sodium hydroborate is found. The process is repeated, charging sufficient diborane (2.3 g.) into the vessel until a pressure of 3 atmospheres (absolute) is reached. After shaking the mixture for 4 hours at 25 C., an increase in pressure is observed on the gauge. Hydrogen is found inrthe volatile reaction products and only 2.1 g of diborane is recovered. Sodium octahydrotriborate (1.0 g.) is isolated from the solid reaction prodpressures, e.g., 5 atmospheres or higher, the reaction proceeds rapidly and good yields ofdesired products are obtained. q

Pressures. above atmospheric can be obtained by any suitable means. Inert gases, e.g., nitrogen, argon, helium,

saturated hydrocarbons, and the like, can be charged into cmmm ug n with ammonia, (NI-I4)2B12H12; with isfunreactive, and it is a-preferred solventj However,

glyme and diborane in the absence of sodium hydroborate react at 100 C. with cleavage of the glyme. Similarly, at low temperatures, i.e., at less than about 80 C., di-

ethyl ether is a satisfactory solvent but at higher temperatures, generally "above 100 C., it shows some cleavage.

obtained from Na B I-I is neutralized by treatment with cesium hydroxide. A white solid precipitates which is separated by filtration and dried as described above. The product, which is Cs B H dicesium dodecahydrododecaborate (2-) is sparingly soluble in water and it is characterized by the following infrared absorption bands: 3.9a, 9.35 sharp, strong; 14.0 sharp, medium; 13.3 4, medium broad, weak.

Analysis.Calcd for Cs B I-I Cs, 65.18; B, 31.84; H, 2.97. Found: Cs, 62.7; B, 30.91, 31.08; H, 3.17.

(C) An aqueous solution of the acid, H B H is neutralized with an aqueous solution of barium hydroxide. The clear neutralized solution is evaporated to dryness under reduced pressure to obtain barium dodecahydrododecaborate as a 'white crystalline residue. The product which has the formula BaB H [barium dodecahydrododecaborate (2)], is very soluble in water and ethyl alco- 1101. The infrared absorption spectrum of the compound shows bands at 4.03 1. and 934a which are within the range of characterizing absorption bands for the B H anion.

Analysis.--Calcd for BaB H /acgH pH-l /aH oz Ba, 42.30; B, 39.99; H, 5.37; C, 2.46. Found: Ba, 42.16; B, 39.61; H, 5.41; C, 2.37.

An aqueous solution of the acid, upon treatment with 'tetramethylammonium chloride or tetramethylammonium hydroxide yields [(CH N] B H In like manner, reaction of the acid with aqueous hydrazine yields (NH NH B H with phenylhydrazine,

with ferous sulfate, FeB H with calcium hydroxide,

C-aB H with cobalt chloride, 'Co(B H withmera curic nitrate, HgB H with-bismuth chloride,

i2( 12 12)3 a with magnesium chloride, MgB H vwith pyridine,

ethylamine, C I-I NH B H with trioctylamine, s 17)s 2B12H12 with w-aminocapronitrile, [CN(CI I NH B H with cyclohexyl amine, (C6H11NH3)2B12H12; amine, [(C -H hNH hB H aand with p-aminobenzoic It is preferable, therefore, to employ'the higherboiling solvents at temperatures above 100 C.

Examples If-XI illustrate princ pally thepreparation of alkali metal dodecanydrododecaborates. The free acid, I

H B H can be prepared from asalt of. this type as illustrated in Example XIII-A below. The acid is then 1 reacted with an appropriate salt or base, as illustrated in i V 3198a and 9,311.. i"

Example XIII-B, to obtain a broad range of the dodecahydrododecaborate anion.

. Example XIII (A) An aqueous solutioii containing 0.43 g. of disodi' I salts having um dodecahydrododecaborate (2%), obtained by the process-described in Example 11, is passed through a 0.5" diameter chromatography column containing ml. of the ion'exchange resin known commercially as .Anib'erlite IR-120-H, acid form. -The strongly acid effluent from' the column is evaporated to remove allmaterials volatile at less than 0.00 1 .mm. at;45 C. There 'remain's'O.'38 g.

dihydrogen dodecahydr'ododecaborate (2%)."

t (13) An aqueous solution fofthe free: :cid; (H B l-ll has the formula H B H shows strong absorption; at 'fl' A broad, range of salts carrbe obt'ained by employing metathetic reactions 'between alkali metal or alkaline earth metaldodecahydrododecaborates and other salts, as

illustratedin Example v Example .XIV; r

(A) An aqueous solutioncontaining'03 g, of disodium dodecahydrod odecaborate, obtained by a process as described in Example II, is mixed with anaqueous solution containing. an equal weight'of tetramethylammonium chloiide. Awhite precipitate forms immediately. The, mixture is heated toboiling and suificient methanol is added to form a clear solution, I The solution is chilled,

' and white crystalsform which ate separated'b'y filtration,

sharp, strong.

washed anddried at very low pressure at C. There is obta'inediO.14 g; of'bis(tetramethylamnionium) dodecahydrodode'caborate (2); f V v fA ndlylsimecalcd for [(CHQZ NJ B HHZ C, 33.11; H,

" 1'1 .5; B, 44.74; .N, f9.65.' ro ndsjc, 30.80; H, 11.77; B,-

y The infrared;absorption spectrum ofthe compound is as follows, usingta Nujolfmull: 3.95a,;sharp, strong; -fine structure at".4.9.-.-6 .5,a,.'Weak-; 7.8g, sharp, medium; 9.4 sharp; strong; and "[forthe CH N+" cation],

The cQfIlPQHHd canbe puritied hyfrecrystallization from water to yield the monohydr'ate:

sharp, medium.

solution of 12 g. of cesium fluoride.

31.13; H, 12.41; B, 42.07; N, 9.08. Found: C, 30.95;

H, 11.48; B, 42.68; N, 8.80, 8.91.

(B) An aqueous solution containing 0.25 g. of disodium dodecahydrododecaborate (2-), obtained by a process as described in Example 11, is treated with an aqueous solution containing 0.25 g. of cesium chloride. A white precipitate forms which redissolves when the mixtureis heated to boiling. Upon chilling, dense White crystals are precipitated which are a mixture of dicesium dodecahydrododecaborate (2-) and cesium chloride. The crystals are separated and dried at 90 C. underreduced pressure (less than 1 mm. of mercury), to obtain 0.31 g. of white crystals. The product can be further purified by recrystallization from water and it has the composition:

The infrared absorption spectrumof a Nujol mullfof the compound shows the following absorption bands; 3.9 1, 4.1 2, doublet, sharp, strong;'9.25n, sharp, strong; 9.45 1, sharp, medium; 13.75 sharp, medium; 1 4.05,u,

Example XV An aqueous solution of 3.2 g. of Na B H (with water and glyme of crystallization, obtained by a process as described in Example II) is mixed with an aqueous cipitate forms which dissolves on warming the reaction mixture. On.coling, fine white crystals form which are separated by filtrationand dried. There. is obtained 3.2 g. cesium dodecahydr'ododecaborate (2 with "solvent (glyme) of crystallization.

Example XVI A solution at 0.891,. of, P,P,P, ',Pflr rhexanj tn i ethylenediphosphoniurn bromide inml; of water is added with stirring to a solution of 1.13 g. of the cesium salt of Example XIIKB) in ,l00 mlto f water. -A voluminous white precipitate forms. The mixture is boiled :to dissolve most of the precipitate." Cooling of the hot-solution results in precipitationof a white solid which is sep a) a 2 2 3 a] 12 12 Theide ntity of the-compound is confirmed-by the infrared spectrum and by.-elemental analysis. The product, as

' obtained, is..free-of waten'of hydration.

" 'Exgr'iz'ple XVII (A) An aqueous solution containing 0.01 mole of Na B H is added with stirring to 13 ml. of an aqueous solution containing,2.2 g. of ZnCl and 7 ml. of concentrated aqueous NH OH. A white solid product precipi tates and it is separated by filtration. 'The. solid product A heavy white pie-' Analysis.Calcd for [Zn(NI-I B H Zn, 23.65; N, 20.4; B, 47.2; H, 8.78. Found: Zn, 23.60; N, 19.55; B, 45.8; H, 8.57.

(B) Using the procedure of Part A, a small quantity of disodium dodecahydrododecaborate is treated with ammoniacal nickel(II) chloride. A lavender-colored solid product precipitates audit is separated by filtration. The product is recrystallized from hot aqueous ammonia solution to form lavender crystals which aredried at 90 C. under very low pressure (less than 0.01 mm. of

mercury) The product is hexaamminenickelfll) dodecahydrororecaborate (2-), i.e.,;a compound of the formula Ni(NH B H' g.' The compound, as obtained under the above conditions of drying, contains 0.5 mole of water of crystallization. The infrared absorption spectrum of thec'ornpound shows absorption bands at 4.02;; and 944 which are characteristic forithe B H anion, 'as

well as other bands at wave lengths which are charac-j teristic tor the hexaamminenickel{ cation.

Analysis.' -Calcd for Ni(NH B H /2H O: Ni, 18.61; N, 26.95; B, 41.6. Found: Ni, 18.81; N, 26.86; B, 41.6.

e 3 A Example XVIII 1 An aqueous solution of 4.4 g. of p-methoxybenzenediazonium tetrafiuoroborate in 50 ml. of water is filtered to remove insoluble material. The filtrate is cooled in an ice bath and an aqueous solution containing 1.0 g. of the monohydrate of disodium dodecahydrododecaborate (Na B l-l -H o) is added to the filtrate withstirring; A heavy white precipitate forms which is separated by filtration. red absorption spectrum shows bands at 4.0; and 9.4

characteristic forth e and-B skeleton structures.

The spectrum also shows bands at 4.4a. (for the diazoniurn structure) and 63 1,91 1 and 1119 (for the aromatic ring structure). The

product is pme thoxybenzcne- .diazonium dodecahydrododecaborate (2*), i.e.

- identity of the compound is confirmed by elemental analysis of-a portion ofthe product which is dried alt 325 C. and 0.02 mm. pressure for 20glrours. The dried product is shock sensitive and it 'detonates with a flash of light and evolution of much black ash when placed on a metal block and struck with a hammer. It also detonates in the combustion chamber employed for analysis but, despite this behavior, analytical data conform reasonably well with theoretical values.

6.36.. .FoundwC, 38.86; 6.26.

" potassium phenoxidedn ethanol solution to'iormasoluis dissolved in about 700ml; of hot aqueous ammonia (4 the solution is chilled. The product crystallizes as glistening white plates which are separated by filtration and dried under reduced pressure (less than 0.011 mm. of mercury) at 90 C. to yield 2.2 g. of the ammonia complex of zinc dodecahydrododecaborate having the structure 'Zn(NH B H which can be called" tetraam- The in.

absorption bands for. the bound NH;

1 parts of'water and .1 part of concentrated NH OH) and: i

tion of intense yellow diazon ium salt. r

.A further characteristic reaction of the diazonium salt of Example XVIII is its rearrangement in 'refiuxin-g ethanol solution to a hydrate of the acid oi an arylazosubstituted polyhydrododecaborate, i.e., a compound of the formula (IIQO)2B12H1Q(N2CQH4OCH3)2. Compound dissolves in ethanol to form a solution of violet color. Evaporationof the solvent leaves-a tacky purple solid. This product is useful as'ia dye for fabrics.

. By using the processes illustrated in Examples XIV,

.XV and XVI, sodium or potassium dodecahydrodec- U aborate can be reacted with rubidium chloride to yield Rb B H12; With strontium chloride to yield SrB H with tantalum chloride to yield Ta(B H with-chromium sulfate to yield Cr (B H with r'nanganous acetate to yield MnB I-I with cupric chloride to yield CuB H with cuprous chloride 'to' yield Cu B H g; withzinc bromideto yield ZnB H ;'with cadmium chloride to yield CdB I-I with" aluminum chloride (hydrated) to yield, Al (B I-l .with stannic chloride to yield Bi (B H .with" benzyltrimcthylammonium The solid product is dried in air and its infracolor, characteristiciof an aromatic 1 16- chloride to yield [(C I-I CH (CH N] B H with The embodiments of the invention in which an exclusive tetra'butylammonium chloride to yield property or privilege is claimed are defined as follows:

c H N B H l. Compounds having the formula 4 9')4 12 12 .12 I MJBIZHIZM v I with tetmmethylphosphomum bromlde to yleld wherein M is a cation having a total atomic weight of at CH P B H 7 least 5 and a valence of less than 5, and a and b vary from H 12 12 12 1 to3 and satisfy the following relation: with methyltriphenylphosphonium bromide to yield axlvalence f M [CH (C H P] B H and with dicyclohexyldihydro- 1O b T genphosphonium bromide to yield [(C H PH B H The reaction can be conducted in ,nonaqueous solvents, for example, methanol, ethanol, ether and the like,'if M 'flg l-i desired.

By using the process of Example XVII with the approl5 priate metal halide there can be obtained a wide variety of metal ammine dodecahydrododecaborates, e.g., with cobalt chloride, [Co(NI- I ]B H is obtained; with e w a valence of M copper chloride, [Cu(NH ]B H is obtained. i 2

By using the process illustrated in Example XVIII-with 2O having the formula the appropriate aryldiazonium halide,a broad range of diazonium salts are obtained,,e.g., with phenyldi'azonium l a i2 12).b chlonde is obtaimd (CBH5N2)2B12H12,, wlth- "wherein M isa cation of a nitrogen base having a molecumiphthyldlazomum bromlde (CWHVNUZBIQHIZ lar weight of from about 17 to 800, anda and b vary tamed; and with p-ethoxyphenyldiazonium chloride, r 1 to 3 and satisfy the following relation: (C2H50c5I'I4N2)2B 2H 2 iS Obtained. w v

2;. Compounds having the formula I wherein M is a metal having an atomic weight of from about 5 to 209, and a and b vary from 1 and 3 and satisfy thefollowing relation;

The dodecahydrododecaborate salts show a remark- 1 b=a valenvce of M able and'unexpected'stability in solution, particularly in v i 2 the presence of inorganic acids. To illustrate, 1.00 g. of 4 fb i d h i h f ul Na B H -fl O is dissolved in 50 m1. of 5% hydrochloric 3O i acid solution. The solution is refluxed for 1 hour and M11 B12H12 b I it is then cooled rapidly and stored at 05 C. After a wherein Mis a cation of a phosphonium base, and a and shgrt period the solution is evaporated to dryness under' b vary froml to 3 and satisfy the following relation: re uced pressure. There is obtained 1.2 g. of white, 1 crystalline residue which is shown by the infrared absorp- 1. b g tion spectrum to be Na B H with a small quantity of e H B H The infrared absorption spectrum shows that 5. Disodium dodecahydrododecaborate (2-). the 3 1-1 anion is unafiected by theacid. 6. Dipotassium dodecahydrododecaborate (2-). The free acid in the form of its hydrate, prepared as 7. Bis(tetramethylammonium) dodecahydrododecab'odescribed in Example XIII, Part A, is "completely stable rate (2-). I v during storage in conventional containers at ordinary Dicesium dodecahydrododecaborate (2-); atmosphere conditions. Even after 32 days standing in 9. The ammonium complex ofzinc dodecahydrododeca closed container, the infrared absorption spectrum is' aborate' (2-) having the structural formula unchanged, showing no evidenceof hydrolysis, oxidation, i VZMNHBMBIQHIZ rearrangement orv decomposition. I M I V p The dodecahydrododecaborate salts are not hydrolyzed dQdWahYdIOHOdeCQbOTaW ggsz by reflujxmg m neutral bolhng waieifor 1 References Cited in" the file of this patent Thisapplication is a continuation-impart of our earlier v UNITED STATES PATENTS filed application Serial No.15,042, filed March 15,1960, 29219-63 Baker Jan 19 1960 and now abandoned. i The foregoing detailed description has been given for OTHER REFERENCES I clearness f understanding y n no unnecessary Hurd: Chemistry of the Hydrides, John Wiley, pp. 81, limitations are to be understood therefrom, The inver'l- 83, August 25, 1952. tion is not limited to the exact details shown and deti m p y c 3314 scribed,-for'obvious modifications willfoccur to; those i b; Abstyacts pf p 133m ACS M eti g I skilled in the art. p p v (San Francisco).'

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,169,045 February 9, 1965 Henry C. Miller et-al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below Column 16, line 15, for "from 1 and 3" read from 1 to 3 v Signed and sealed this 29th day of June 1965.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Altcsting Officer Commissioner of Patents Patent No. 3,169, 045 February 9 1965 Henry C. Miller et a1 It is hereby certified that error a ent requiring correction and that th corrected below.

ppears in the above numbered pate said Letters Patent should read as Column 16 line 15 for "from 1 and 3" read from 1 to 3 Signed and sealed this 29th day of June 1965.

SEAL) Attest:

ERNEST W. SWI DER Attesting Officer EDWARD J. BRENNER Commissioner of Patents 

1. COMPOUNDS HAVING THE FORMULA 